endo-3,3-Dimethyl-4-oxobicyclo­[3.1.0]hexan-2-yl methane­sulfonate

The relative configuration of the endo isomer of the title compound, C₉H₁₄O₄S, has been established and the conformation of the diastereoisomer is discussed. The five-membered ring adopts an envelope conformation. The conformation of the methane­sulfonate substituent is stabilized by inter­molecular C—H...O hydrogen bonds. The crystal packing results in alternating layers of polar methane­sulfonates and stacked bicyclo­hexa­nyl rings parallel to ab.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.046
• wR factor = 0.130
• Data-to-parameter ratio = 26.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        365

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT793_ALERT_4_G The Model has Chirality at C1      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C4      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C5      (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the course of a work involving the enantioselective synthesis of didesmethyl-deltametrinic acid (Krief et al., 2000; Krief, 1994) both the exo and endo isomers of 3,3-dimethyl-4-oxobicyclo[3.1.0]hexan-2-yl methanesulfonate were synthesized and characterized.

The X-ray crystallography study reported here determined the relative stereochemistry of the endo diasteroisomer : C(1) S, C(4) R, and C(5) R. The compound crystallizing in a centrosymetric space group, one obtains the racemic mixture S,R,R/R,S,S.

The five-membered ring C1—C5 adopts an envelope conformation. Puckering parameter Phi is 260.1 (8)° and close to the expected value of k x 36° (Cremer & Pople, 1975), suggesting that the presence of a sp² carbon (C2) in the five-membered ring does not significantly distort its conformation. The observed values of torsion angles defining the C1—C5 ring (Table 1) fairly well follow the theoretical sequence of torsion angles -ω1, ω2, -ω2, ω1 and 0 (Dunitz, 1979) characteristic of an envelope conformation.

Atom C6 of the fused three-membered ring deviates by +1.250 (2) Å from the mean plane defined by the five atoms of the C1—C5 ring (Figure 1).

Steric effects resulting from C6 being in cis of the mesylate substituent on O2, constrain the conformation of the methanesulfonate group. Positions of the oxygen atoms O3 and O4 of the sulfonate group are further explained by intra and intermolecular CH···O hydrogen bondings. Indeed O3 forms an intramolecular H bond [O3···H4 = 2.81 Å] with H4 of C4 that carries the mesylate. An intermolecular H bond with H4 further involves O4 [C(4)—H4 ··· O4_i: D···A = 3.302 (4) Å; H···A = 2.48 Å; D - H···A = 141°, i = x-1,y,z].

Packing is also reinforced by van der Waals interactions resulting in alterning layers of polar methanesulfonates and stacked bicyclohexanyl rings parallel to the ab cell planes.

Related literature

For related enantioselective syntheses, see : Krief (1994); Krief et al. (2000). For puckering parameters and theoretical torsion angles, see: Cremer & Pople (1975); Dunitz (1979).

S2. Experimental

Synthesis of the compound will be detailed elsewhere.

Crystals were obtained by evaporation at 5°C of solutions in diethylether.

S3. Refinement

All H atoms were placed at idealized positions and allowed to ride on their parent atoms, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene groups and U_iso(H) = 1.5U_eq(C) for the methyl group.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. Conformation (ORTEP view) of the title compound. Only H atoms on chiral carbons have been retained for clarity. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

endo-3,3-Dimethyl-4-oxobicyclo[3.1.0]hexan-2-yl methanesulfonate

Crystal data

C9H14O4S	Z = 2
Mr = 218.27	F(000) = 232
Triclinic, P1	Dx = 1.395 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8558 (3) Å	Cell parameters from 2686 reflections
b = 7.7497 (4) Å	θ = 3.2–32.6°
c = 12.2527 (6) Å	µ = 0.30 mm^−1
α = 84.290 (4)°	T = 293 K
β = 79.531 (4)°	Prism, colorless
γ = 72.070 (5)°	0.35 × 0.14 × 0.12 mm
V = 519.66 (5) Å^3

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini ultra Mo) detector	3432 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 10.3712 pixels mm^-1	θmax = 32.6°, θmin = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→11
Tmin = 0.904, Tmax = 0.966	l = −18→18
6128 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0721P)^2] where P = (Fo^2 + 2Fc^2)/3
3432 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1819 (3)	0.4668 (2)	0.66360 (15)	0.0492 (4)
H1	0.0668	0.4050	0.6508	0.059*
C2	0.1965 (3)	0.6346 (2)	0.59887 (13)	0.0422 (3)
C3	0.2668 (3)	0.75983 (19)	0.66753 (13)	0.0377 (3)
C4	0.2405 (3)	0.6746 (2)	0.78727 (12)	0.0383 (3)
H4	0.0950	0.7502	0.8323	0.046*
C5	0.2143 (3)	0.4885 (2)	0.78131 (14)	0.0474 (4)
H5	0.1187	0.4400	0.8439	0.057*
C6	0.4088 (4)	0.3618 (2)	0.70955 (15)	0.0534 (4)
H6A	0.4345	0.2330	0.7265	0.064*
H6B	0.5558	0.3956	0.6814	0.064*
C7	0.5212 (3)	0.7725 (3)	0.61787 (15)	0.0556 (5)
H7A	0.6366	0.6539	0.6194	0.083*
H7B	0.5646	0.8515	0.6606	0.083*
H7C	0.5216	0.8202	0.5425	0.083*
C8	0.0812 (4)	0.9504 (2)	0.66350 (19)	0.0642 (5)
H8A	0.1226	1.0300	0.7066	0.096*
H8B	−0.0787	0.9425	0.6935	0.096*
H8C	0.0843	0.9972	0.5879	0.096*
C9	0.2608 (3)	0.7738 (2)	1.04091 (14)	0.0503 (4)
H9A	0.2548	0.8619	1.0920	0.075*
H9B	0.3173	0.6540	1.0740	0.075*
H9C	0.1012	0.7930	1.0235	0.075*
O1	0.1502 (3)	0.67456 (18)	0.50596 (10)	0.0606 (4)
O2	0.4535 (2)	0.64888 (14)	0.84223 (9)	0.0421 (3)
O3	0.3691 (3)	0.97232 (17)	0.87030 (11)	0.0717 (4)
O4	0.7018 (2)	0.7375 (2)	0.94357 (12)	0.0761 (5)
S1	0.45905 (8)	0.79673 (6)	0.91953 (3)	0.04398 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0598 (11)	0.0458 (9)	0.0546 (10)	−0.0288 (8)	−0.0180 (8)	−0.0019 (7)
C2	0.0405 (8)	0.0438 (8)	0.0452 (8)	−0.0140 (7)	−0.0116 (6)	−0.0025 (7)
C3	0.0408 (8)	0.0344 (7)	0.0426 (8)	−0.0156 (6)	−0.0133 (6)	0.0027 (6)
C4	0.0353 (7)	0.0398 (8)	0.0421 (8)	−0.0143 (6)	−0.0058 (6)	−0.0031 (6)
C5	0.0589 (10)	0.0487 (9)	0.0438 (9)	−0.0314 (8)	−0.0089 (7)	0.0059 (7)
C6	0.0680 (12)	0.0369 (8)	0.0601 (11)	−0.0172 (8)	−0.0211 (9)	0.0017 (7)
C7	0.0600 (11)	0.0673 (12)	0.0508 (10)	−0.0390 (10)	−0.0052 (8)	0.0036 (9)
C8	0.0767 (14)	0.0400 (9)	0.0783 (13)	−0.0074 (9)	−0.0359 (11)	−0.0025 (9)
C9	0.0526 (10)	0.0515 (10)	0.0414 (8)	−0.0116 (8)	0.0001 (7)	−0.0030 (7)
O1	0.0771 (9)	0.0638 (8)	0.0499 (7)	−0.0244 (7)	−0.0290 (6)	0.0015 (6)
O2	0.0476 (6)	0.0399 (6)	0.0409 (6)	−0.0116 (5)	−0.0131 (5)	−0.0061 (4)
O3	0.1261 (14)	0.0447 (7)	0.0544 (8)	−0.0425 (8)	−0.0113 (8)	0.0004 (6)
O4	0.0484 (8)	0.1248 (13)	0.0661 (9)	−0.0348 (8)	−0.0039 (6)	−0.0363 (9)
S1	0.0507 (3)	0.0491 (2)	0.0385 (2)	−0.02405 (19)	−0.00324 (16)	−0.00920 (16)

Geometric parameters (Å, º)

C1—C2	1.472 (2)	C6—H6B	0.9700
C1—C6	1.503 (2)	C7—H7A	0.9600
C1—C5	1.521 (2)	C7—H7B	0.9600
C1—H1	0.9800	C7—H7C	0.9600
C2—O1	1.2066 (19)	C8—H8A	0.9600
C2—C3	1.534 (2)	C8—H8B	0.9600
C3—C7	1.532 (2)	C8—H8C	0.9600
C3—C8	1.543 (2)	C9—S1	1.7429 (17)
C3—C4	1.549 (2)	C9—H9A	0.9600
C4—O2	1.4747 (17)	C9—H9B	0.9600
C4—C5	1.506 (2)	C9—H9C	0.9600
C4—H4	0.9800	O2—S1	1.5687 (11)
C5—C6	1.467 (3)	O3—S1	1.4156 (14)
C5—H5	0.9800	O4—S1	1.4287 (14)
C6—H6A	0.9700
C2—C1—C6	114.72 (14)	C1—C6—H6A	117.6
C2—C1—C5	107.13 (13)	C5—C6—H6B	117.6
C6—C1—C5	58.06 (11)	C1—C6—H6B	117.6
C2—C1—H1	120.3	H6A—C6—H6B	114.7
C6—C1—H1	120.3	C3—C7—H7A	109.5
C5—C1—H1	120.3	C3—C7—H7B	109.5
O1—C2—C1	125.52 (15)	H7A—C7—H7B	109.5
O1—C2—C3	123.47 (14)	C3—C7—H7C	109.5
C1—C2—C3	110.94 (13)	H7A—C7—H7C	109.5
C7—C3—C2	109.53 (13)	H7B—C7—H7C	109.5
C7—C3—C8	109.33 (15)	C3—C8—H8A	109.5
C2—C3—C8	108.62 (13)	C3—C8—H8B	109.5
C7—C3—C4	115.62 (13)	H8A—C8—H8B	109.5
C2—C3—C4	103.93 (11)	C3—C8—H8C	109.5
C8—C3—C4	109.53 (14)	H8A—C8—H8C	109.5
O2—C4—C5	106.44 (12)	H8B—C8—H8C	109.5
O2—C4—C3	113.84 (11)	S1—C9—H9A	109.5
C5—C4—C3	108.08 (12)	S1—C9—H9B	109.5
O2—C4—H4	109.5	H9A—C9—H9B	109.5
C5—C4—H4	109.5	S1—C9—H9C	109.5
C3—C4—H4	109.5	H9A—C9—H9C	109.5
C6—C5—C4	116.56 (15)	H9B—C9—H9C	109.5
C6—C5—C1	60.38 (11)	C4—O2—S1	120.23 (9)
C4—C5—C1	108.34 (13)	O3—S1—O4	119.56 (10)
C6—C5—H5	119.1	O3—S1—O2	110.12 (7)
C4—C5—H5	119.1	O4—S1—O2	103.74 (8)
C1—C5—H5	119.1	O3—S1—C9	108.61 (9)
C5—C6—C1	61.56 (12)	O4—S1—C9	108.62 (9)
C5—C6—H6A	117.6	O2—S1—C9	105.24 (8)
C6—C1—C2—O1	127.22 (19)	C8—C3—C4—C5	128.36 (15)
C5—C1—C2—O1	−170.65 (18)	O2—C4—C5—C6	−66.42 (17)
C6—C1—C2—C3	−55.74 (19)	C3—C4—C5—C6	56.24 (18)
C5—C1—C2—C3	6.39 (18)	O2—C4—C5—C1	−131.81 (14)
O1—C2—C3—C7	−70.5 (2)	C3—C4—C5—C1	−9.15 (18)
C1—C2—C3—C7	112.43 (15)	C2—C1—C5—C6	−108.87 (16)
O1—C2—C3—C8	48.9 (2)	C2—C1—C5—C4	1.83 (19)
C1—C2—C3—C8	−128.22 (16)	C6—C1—C5—C4	110.70 (16)
O1—C2—C3—C4	165.44 (17)	C4—C5—C6—C1	−96.92 (16)
C1—C2—C3—C4	−11.67 (17)	C2—C1—C6—C5	95.46 (16)
C7—C3—C4—O2	10.41 (18)	C5—C4—O2—S1	−146.30 (11)
C2—C3—C4—O2	130.47 (12)	C3—C4—O2—S1	94.74 (13)
C8—C3—C4—O2	−113.62 (15)	C4—O2—S1—O3	−42.98 (13)
C7—C3—C4—C5	−107.61 (15)	C4—O2—S1—O4	−172.07 (11)
C2—C3—C4—C5	12.45 (16)	C4—O2—S1—C9	73.90 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4^i	0.98	2.48	3.302 (4)	141
C9—H9B···O2^ii	0.96	2.54	3.485 (2)	169

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2.